美国加州理工学院Gregory C. Fu团队取得一项新突破。他们研究出光诱导铜催化烷基卤化物脱羧。2025年4月2日出版的《自然》杂志发表了这项成果。

在这里，该团队描述了一种解决这些挑战的简单方法，主题是手性铜催化剂，由市售成分原位生成，通过碳-卤素键裂解实现叔（和仲）烷基卤化物的光诱导离中心化。机理研究（包括假设中间体的独立合成，光物理，光谱和反应性研究，以及密度泛函理论计算）为他们提出的催化循环中的关键步骤和中间体提供了支持，以及对映体选择性的起源的见解。

据介绍，脱消旋是一种新兴的生成对映体富集化合物的策略，其中容易获得的外消旋起始材料的两个对映体转化为单个对映体，通常通过光诱导催化剂的作用。这种潜在的强大的不对称催化方法的原理证明已经被描述了；然而，实质性的挑战尚未得到解决，包括利用碳杂原子（而不仅仅是碳-氢和碳-碳）键裂解来实现去消酰基化，以及开发提供广泛类别的主题对映体富集化合物和四取代立体中心的工艺。

附：英文原文

Title: Photoinduced copper-catalysed deracemization of alkyl halides

Author: Zhong, Feng, Li, Renhe, Mai, Binh Khanh, Liu, Peng, Fu, Gregory C.

Issue&Volume: 2025-04-02

Abstract: Deracemization is an emerging strategy for generating enantioenriched compounds wherein the two enantiomers of a readily available racemic starting material are transformed into a single enantiomer, typically through the action of a light-induced catalyst1,2. Excellent proof of principle for this potentially powerful approach to asymmetric catalysis has been described3,4,5,6,7,8; nevertheless, substantial challenges have not yet been addressed, including the exploitation of carbon–heteroatom (rather than only carbon–hydrogen and carbon–carbon) bond cleavage to achieve deracemization, as well as the development of processes that provide broad classes of useful enantioenriched compounds and tetrasubstituted stereocentres. Here we describe a straightforward method that addresses these challenges, using a chiral copper catalyst, generated in situ from commercially available components, to achieve the photoinduced deracemization of tertiary (and secondary) alkyl halides through carbon–halogen bond cleavage. Mechanistic studies (including the independent synthesis of postulated intermediates, photophysical, spectroscopic and reactivity studies, and density functional theory calculations) provide support for the key steps and intermediates in our proposed catalytic cycle, as well as insight into the origin of enantioselectivity.

DOI: 10.1038/s41586-025-08784-8

Source: https://www.nature.com/articles/s41586-025-08784-8